Dyeing a mixed fibre fabric of cellulose/polyacrylonitrile of cellulose/acid-modified polyester with a reactive dye and a basic dye

ABSTRACT

A mixed fabric of hydroxy group-containing fibers and cyano and/or carboxy group-containing fibers, the hydroxy group-containing fibers having been dyed with a reactive dye, is aftertreated with a product of reacting a mono- or polyfunctional amine having one or more primary, secondary and/or tertiary amino groups with cyanamide, dicyandiamide guanidine or bis-guanidine, said product containing at least one reactive hydrogen atom linked to a nitrogen atom, and is then dyed with a basic dye.

According to the invention, there is provided a process for dyeing amixed fibre fabric of hydroxy-group-containing and cyano- and/orcarboxy-group-containing fibres characterised by

(a) aftertreating the hydroxy-group-containing fibres of the fabric,which fibres have been dyed with a reactive dye, with a polymericreaction product A (herein defined as Product A), product A being theproduct of reacting a mono- or poly-functional amine having one or moreprimary and/or secondary and/or tertiary amino groups with cyanamide,dicyandiamide, guanidine or bisguanidine (in which up to 50 mole percentof the cyanamide, di-cyandiamide, guanidine or bisguanidine may bereplaced by a dicarboxylic acid or mono- or di-ester thereof) wherebyammonia splits off (optionally in the presence of a catalyst); saidproduct A containing at least one free hydrogen atom linked to anitrogen atom; and

(b) dyeing the fabric, following aftertreatment with Product A, with abasic dyestuff.

Preferably the hydroxy-group-containing fibres are cellulose (e.g.cotton) and the cyano- and/or carboxy-group containing fibres arepolyacrylonitrile or acid modified polyester fibres.

Preferably the mixed fibre fabric is cotton/polyacrylonitrile orcotton/acid modified polyester.

Product A is known and is described, together with methods forpreparation, e.g. in U.S. Pat. No. 4,410,652 and U.S. Pat. No. 4,764,585(=GB Patent Application 2,163,760 A); the contents and preferences ofthe said U.S. patents are incorporated herein by reference.

The catalysts that can be used for the production of Product A are thosedefined as catalyst K in U.S. Pat. No. 4,764,585 and GB PatentApplication 2,163,760 A, the description of which is incorporated hereinby reference from these patent specifications.

The reactive dyes that can be used to dye the hydroxy-group-containingfibres in a process according to the invention are preferably thosedefined as Reactive Dyes in the Colour Index, more preferably thosereactive dyes defined in U.S. Pat. No. 4,764,585.

The basic dyes that can be used to dye the cyano- and/or carboxygroup-containing fibres are preferably those defined in the Colour Indexas Basic Dyes, more preferably those Basic dyes defined in U.S. Pat. No.3,852,261.

The hydroxy-group-containing fibres are dyed by immersing the fabric ina first dyeing bath containing the reactive dye or dyes and dyeing iscarried out at elevated temperatures (e.g. 70°-80° C.) and then coldwashed.

The fabric is then preferably immersed in a second bath containing theaftertreatment Product A according to known methods (for example asgiven in the dyeing examples of U.S. Pat. No. 4,764,585). Aftertreatmentis preferably carried out at 20°-70° C., more preferably 60° C.

Dyeing of the cyano- and/or carboxy-group-containing fibres is carriedout in a third bath containing basic dyes by known methods, for exampleaccording to U.S. Pat. No. 3,852,261, the content of which isincorporated herein by reference.

The present invention alleviates the problem that reactive dyes on thecotton fibres of a mixed fabric of cotton/polyacrylonitrile tend (withthe exception of a select number of reactive dyes) to have a stainingeffect on the polyacrylonitrile and that there is a strong smudgingeffect of the basic dyes on the cellulose part of the mixed fibrefabric.

The dyeings so produced have good fastness properties and are leveldyeings. The present invention also alleviates the time consumingsoaping needed to remove the unbound reactive dye resulting from dyeing.

The invention will now be illustrated by the following Examples in whichall parts and percentages are by weight, all temperatures are in °C. andall percentages are based on the weight of substrate unless indicated tothe contrary.

EXAMPLE 1

100 Parts of a 50:50 mixed fibre fabric of cotton/polyacrylonitrile aredyed from an aqueous exhaust bath with 0.18% C.I. Reactive Yellow 58,0.12% C.I. Reactive Yellow 29 and 2.2% C.I. Reactive Blue 18conventionally.

The fabric that has been dyed with the reactive dyes (only the cottonpart is dyed) is then treated in an aftertreatment bath containing 2% ofthe compound of Example 1 of GB Published Patent Application No.2,163,760 A (=U.S. Pat. No. 4,764,585).

The fabric is then washed for 2 minutes and is then dyed in a furtheraqueous bath containing 0.05% of the dyestuff of formula 1a ##STR1##0.02% of C.I. Basic Yellow 82; and 0.12% of the compound of formula 1b##STR2##

This produces a fabric having a level dyeing and good wet fastnessproperties.

EXAMPLE 2

A mixed fibre fabric (50:50 cotton/polyacrylonitrile) as in Example 1 isdyed with 1.1% C.I. Reactive Yellow 41, 1.6% C.I. Reactive Red 56 and0.41% C.I. Reactive Blue 17.

The dyed fabric is then treated with the aftertreatment product ofExample 1 according to Example 1.

The treated fabric is then dyed with 0.21% C.I. Basic Yellow 82, 0.14%of the dyestuff of formula 2a ##STR3## and 0.046% of the dyestuff offormula 2b ##STR4##

This produces a fabric having a level dyeing with good wet-fastnessproperties.

EXAMPLES 3 TO 15

100 Parts of a mixed fibre fabric (50:50 cotton/polyacrylonitrile) isdyed using reactive dyes as listed in Table 1 below by immersing thefabric in an aqueous exhaust bath (Bath 1) conventionally, therebydyeing the cotton.

The dyed fabric is then immersed in an aqueous bath containing 2% of theAftertreatment Agent of Example 1 (i.e. the compound of Example 1 of GBPublished Patent Application 2,163,760 A). The treated fabric is thenwashed for 2 minutes.

The fabric is then immersed in a third aqueous dyebath (Bath 3)containing the Basic dyes as given in the Table below. Level, wet fastdyeings result.

                  TABLE                                                           ______________________________________                                        Ex-                                 Colour                                    am-  Reactive Dyes  Basic Dyes of   of                                        ple  of Bath 1      of Bath 3       Dyeing                                    ______________________________________                                        3.   2%      CI Reactive                                                                              0,35% CI Basic  Gold                                               Yellow 125       Yellow 82 Yellow                                4.   1%      CI Reactive                                                                              0,17% CI Basic  Brillant                                           Orange 64        Yellow 82 Red                                        1,1%    CI Reactive                                                                              0,75% CI Basic                                                     red 159          Red 104                                         5.   0,31    CI Reactive                                                                              0,12% CI Basic  Navy                                               Orange 69        Yellow 82 blue                                       0,85%   CI Reactive                                                                              0,09% CI Basic                                                     Red 159          Red 104                                              1,4%    CI Reactive                                                                              0,3%  CI Basic                                                     Blue 193         Blue 41:1                                       6.   0,09%   CI Reactive                                                                              0,005%                                                                              CI Basic                                                     Red 147          Yellow 82 Blue                                       2%      CI Reactive                                                                              0,012%                                                                              CI Basic                                                     Blue 114         Red 104                                                                 0,2%  CI Basic                                                                      Blue 41:1                                       7.   2,5%    CI Reactive                                                                              0,175%                                                                              CI Basic  Tur-                                               Blue 41          Blue 3    quoise                                8.   2,25%   CI Reactive                                                                              0,08% CI Basic                                                     Blue 41          Yellow 13                                            1,25%   CI Reactive                                                                              0,022%                                                                              CI Basic  Brillant                                           Green 12         Blue 41:1 Green                                                         0,14% CI Basic                                                                      Blue 3                                          9.   1,75%   CI Reactive                                                                              0,25% CI Basic  Brown                                              Orange 11        Yellow 82                                            0,95%   CI Reactive                                                                              0,1%  CI Basic                                                     Red 55           Red 104                                              0,2%    CI Reactive                                                                              0,034%                                                                              CI Basic                                                     Blue 52          Blue 41:1                                       10.  2,3%    CI Reactive                                                                              0,08% CI Basic  Green                                              Green 15         Yellow 82                                                               0,12% CI Basic                                                                      Blue 41:1                                       11.  0,5%    CI Reactive                                                                              0,1%  CI Basic  Anthra-                                            Orange 11        Yellow 82 cite                                       0,43%   CI Reactive                                                                              0,05% CI Basic                                                     Red 55           Red 104                                              1%      CI Reactive                                                                              0,15% CI Basic                                                     Blue 214         Blue 41:1                                       12.  1,2%    Reactive   0,15% CI Basic  Golden                                             Orange 74        Yellow 82 Yellow                                13.  1,4%    Reactive   0,4%  CI Basic  Brown                                              Orange 91        Yellow 28                                                                     (48'054)                                             0,4%    Reactive                                                                      Red 184    0,18% CI Basic                                                                      Red 46                                               0,25%   Reactive   0,11% CI Basic                                                     Blue 182         Blue 41(11'105)                                 14.  as in   Example 13 0,78% CI Basic  Brown                                                               Yellow 77                                                               0,28% CI Basic                                                                      Red 51                                                                  0,08% CI Basic                                                                      Blue 124                                        15.  0,6%    CI Reactive                                                                              0,15% CI Basic  Yellow-                                            Orange 14        Yellow 82 ish                                                (19'138)                   Orange                                ______________________________________                                    

What is claimed is:
 1. A process for dyeing a mixed fibre fabric ofhydroxy-group-containing and cyano- and/or carboxy-group-containingfibres characterised by(a) aftertreating the hydroxy-group-containingfibres of the fabric, which fibres have been dyed with a reactive dye,with a polymeric Product A which is the product of reacting a mono- orpoly-functional amine having one or more primary and/or secondary and/ortertiary amino groups with cyanamide, dicyandiamide, guanidine orbisguanidine (in which up to 50 mole percent of the cyanamide,di-cyandiamide, guanidine or bisguanidine may be replaced by adicarboxylic acid or mono- or di-ester thereof) whereby ammonia splitsoff, said Product A containing at least one free hydrogen atom linked toa nitrogen atom; and (b) dyeing the fabric, following aftertreatmentwith Product A, with a basic dyestuff.
 2. A process according to claim1, in which the mixed fibre fabric is cellulose/polyacrylonitrile orcellulose/acid modified polyester.
 3. A process according to claim 2, inwhich the mixed fibre fabric is cotton/polyacrylonitrile.
 4. A processaccording to claim 1, in which the aftertreatment is carried out at atemperature of from 20° to 70° C. inclusive.
 5. A process according toclaim 1 comprising:(a) dyeing the hydroxy-group containing fibres of thefabric with a reactive dye in a first bath; (b) aftertreating thehydroxy-group-containing fibres of the fabric with polymeric reactionProduct A defined in claim 1 in a second bath; and (c) dyeing thefabric, following aftertreatment with Product A with a basic dyestuff ina third bath.
 6. A process according to claim 1 wherein Product A is aproduct of reacting an amine of formula I or II

    R--NH--R                                                   (I)

    RRN--(Z--X).sub.n --Z--NR                                  (II)

in which each R, independently, is hydrogen or a C₁₋₁₀ alkyl groupunsubstituted or monosubstituted by hydroxy, C₁₋₄ alkoxy or cyano, n isa number from 0 to 100, Z, or each Z independently when n>0, is C₂₋₄alkylene or hydroxyalkylene and X, or each X independently when n>1, is--O--, --S-- or --NR-- where R is as defined above, provided that theamine of formula II contains at least one reactive --NH-- or NH₂ group,with cyanamide, dicyandiamide or guanidine in a mol ratio of 0.1 to 1mol of cyanamide, dicyandiamide or guanidine per mol of reactive --NH--or --NH₂ groups.
 7. A process according to claim 5 wherein Product A isa product of reacting an amine of formula I or II

    R--NH--R                                                   (I)

    RRN--(Z--X).sub.n --Z--NRR                                 (II)

in which each R, independently, is hydrogen or a C₁₋₁₀ alkyl groupunsubstituted or monosubstituted by hydroxy, C₁₋₄ alkoxy or cyano, n isa number from 0 to 100, Z, or each Z independently when n>0, is C₂₋₂₄alkylene or hydroxyalkylene and X, or each X independently when n>1, is--O--, --S-- or --NR-- where R is as defined above, provided that theamine of formula II contains at least one reactive --NH-- or NH₂group,with cyanamide, dicyandiamide or guanidine in a mol ratio of 0.1to 1 mol of cyanamide, dicyandiamide or guanidine per mol of reactive--NH-- or --NH₂ groups.
 8. A process according to claim 6 whereinProduct A is a product of reacting diethylene triamine or triethylenetetramine with dicyandiamide.
 9. A process according to claim 7 whereinProduct A is a product of reacting diethylene triamine or triethylenetetramine with dicyandiamide.
 10. A process according to claim 1 whereinProduct A is produced by reacting the amine with cyanamide,dicyandiamide, guanidine or bis-guanidine in the presence of a catalystselected from metals of Group II or III of the periodic table, salts ofsaid metals and pyridines substituted by a tertiary amino group.
 11. Aprocess according to claim 5 wherein Product A is produced by reactingthe amine with cyanamide, dicyandiamide, guanidine or bis-guanidine inthe presence of a catalyst selected from metals of Group II or III ofthe periodic table, salts of said metals and pyridines substituted by atertiary amino group.
 12. A process according to claim 6 wherein ProductA is a product of reacting the amine with cyanamide, dicyandiamide orguanidine in the presence of a catalyst selected from metals of Group IIor III of the periodic table, salts of said metals and pyridinessubstituted by a tertiary amino group.
 13. A process according to claim7 wherein Product A is a product of reacting the amine with cyanamide,dicyandiamide or guanidine in the presence of a catalyst selected frommetals of Group II or III of the periodic table, salts of said metalsand pyridines substituted by a tertiary amino group.
 14. A processaccording to claim 9 wherein Product A is a product of reactingdiethylene triamine or triethylene tetramine with dicyandiamide in thepresence of 0.01 to 10% by weight zinc chloride based on the totalweight of the amine and dicyandiamide.
 15. A process according to claim6 wherein the fabric is cellulose/polyacrylonitrile or cellulose/acidmodified polyester and the aftertreatment is carried out at atemperature of 20° to 70° inclusive.
 16. A process according to claim 7wherein the fabric is cellulose/polyacrylonitrile or cellulose/acidmodified polyester and the aftertreatment is carried out at atemperature of 20° to 70° inclusive.
 17. A process according to claim 12wherein the fabric is cellulose/polyacrylonitrile or cellulose/acidmodified polyester and the aftertreatment is carried out at atemperature of 20° to 70° inclusive.
 18. A process according to claim 14wherein the fabric is cellulose/polyacrylonitrile or cellulose/acidmodified polyester and the aftertreatment is carried out at atemperature of 20° to 70° inclusive.
 19. A mixed fiber fabric dyed bythe process of claim
 7. 20. A dyed fabric produced by the process ofclaim 17.